Hydrocarbon conversion process



- June 22, 1943.

HYDROCARBON CONVERSION PROCESS Filed Nov. 29, 1959 FIG. l

i REACTOR s HEATER s 9 wss 'o 'I HEATER 9 illo I I.

| I I I I I 5J l I HEATER I sJ I 9 6-.Il i lo l I l 4' F`| 7 I I I f. l esl I ,3 Sheets-Sheet l `INvENToR Lows s.KAssEL Filed Nov. 29, 1939 s sheets-sheet 2 Patented June 22,

Louis S. Kassel, Chicago,` Ill.,

versal Oil- Products Company, corporation of Delaware assignor to '(lnl-- s Chicago, lll., a.

Application November '29, 1939, Serial No. 306,63

(ci. 19e-49) 2 Claims.

This application is a continuation-impart of my co-pending application, Serial No. 274,178, flied May 17, 1938, now U. S. lPatent 2,271,646.

This invention relates to an improved method for accomplishing successive contact catalytic reactions wherein different catalysts are employed in some regular sequence, the position of each of the contactmasses being contingent upon* the dependent relation of` one reaction to the other, the conditions employed, and the optimum conditions for each reaction.

The invention is particularly applicable in processes involving a. combination of reactions,

either endothermic orfexotherrnic7 or both or, in some cases, reactions where the heat ofA/reaction is substantially zro, which reactions may be conducted at substantiallythe same conditions of temperature and pressure and where the different reactions are an essential feature in producing the desired result. A

All of the reactions involved in any particular combination, hereafter referred to as a stage,

`are preferably conducted under adiabatic conditions with means provided for tempering or re adjusting the temperature of the reactants between the various stages in processes involving more than one stage. 'Ihe invention may employ, for example, a process involving both dehyeither of the come more and more refractory as the treatment progresses. Between each stage of the process, therefore, a heating zone is preferably employed and the number of stages determines the number of heating zones. 1 1

Other treatments which may advantageously be accomplished, according to the objects of this invention, include the process which involves a combination of catalysts most suitable for cony' ducting, first, dehydrogenatiorr'of aliphatic hy-" drocarbons followed by cyclization of the dehydrogenated products to produce aromaticehydrov carbons.

The invention,v however, is not limited to the particular combinations herein disclosed but may be employed in any combination of endothermic catalytic reactions or combination -of above named reactions with reactions wherein the heat of reaction is substantially zero. combinationsinvolving exotherdrogenation and catalytic cracking, which reactions are both endothermic., In this case, since better results may be obtained in the cracking of olefins as compared to the cracking of parains, it would be desirable to subject the reactants rst to dehydrogenation followed by -catalytic cracking of the conversion products from vthe first step.

In `reactions conducted under adiabatic conditions, the heat of conversion is' ordinarily ob tained from the materials undergoing conversion and the temperature, therefore, of these materials is lcwered and is substantially directly proportional to theamount of material being con-y verted. It is desirable, therefore, to employ rely -atively shallow beds of catalytic material and relatively short contact times 1n order that the temperature is not lowered more than a predetermined value. Therefore, after one particular combination of reactions has been completed inv one stage of the process and the temperature lowered to some predetermined value, the conversion products leaving the last reaction zone are preferably conducted to a heating zone where they are aganraised to the same temperature I es the material entering the system or to. a higher` temperature, since the reaction products beywhich isan example of an .the deposition thereon of the rcase of the latter, the Y mic-reactins, it is understood, of course, that inplace of the heating zone between each stage a cooling zone will be employed in its place.

In processes employing catalysts to assist in the conversion reaction, such as, for example, in polymerization, which is a good example of an exothermic reaction, and c atalytic cracking,

the activity of the catalyst deteriorates, due to carbonaceous materials. However, in depositionl is quite rapid, where in the case of the former the deposition is much slower. In order to ,obtain best results, the catalysts are alternately subjected to processing and reactivation, and inthe case' of polymerization, hydrogenation, and other reactions both the processing andjreactivation would be exothermic, where in the case of catalytic cracking, dehydrogenation, and other related treatments the processing would be endothermic and reactivation exothermic. Reactivation of the catalyst may be accomplishedby passing a stream of heated relatively inert gases containing controlled amounts of air` through the catalyst bed. lThe burning of the carbonaceous material beingexothermic,some form of temperature control is lrequired for preventing excessive heating of the catalystpar.

ticles and consequent destruction of their catalytic activity.

Catalytic cracking, dehydrogenatiom' and cyclization are good examples of the type of conversion reaction to which the invention is par- 'ticularly' well adapted, because in these reactions, due to the rapid deposition of carbonaceous ma terials, the processing-and reactivation is ordiendothermic reaction, A

narily carried out on a cyclic basis, the catalyst being periodically alternated from processing to reactivation and vice versa.

-When endothermic or exothermic reactions, such as those above mentioned, are conducted by contacting the reactants with a mass of catalytic material in the manner heretofore commonly employed, the design of the apparatus, particularly with respect to the size of the zone or zones containing the catalytic material, is limited to heat transfer requirements in order to adequately control the reaction temperature. For example, it is customary to dispose the catalytic material in a plurality of tubular elements connected for parallel flow of the reactants therethrough and to bathe the tubes in a fluid heating or cooling medium depending. upon whether the reaction is endothermic or exothermic. In such cases, the diameter of each tube is limited to' that which will give a good rate oi' heat transfer from the catalyst bed disposed therein and reactants passing therethrough to the cooling medium surrounding the tubes, or from the heating medium surrounding the tubes to the reactants and catalyst.

Increased capacity cannot be obtained with the same degree of control, except by increasing the .number of parallel tubes employed, without increasing their size. Reactors embodying this type of design become extremely cumbersome and expensive with the high charging stock capacities which are ordinarily desired for commercial operation, with the result that the economies one would expect from large scale operations are not attained. The commercial operation becomes more complicated when attempting to accomplish the combination of reactions with which this invention is most largely concerned `in reactors of the type referred to above. Y

The invention involved in my previous application, Serial No. 274,178, now U. S. Patent 2,271,646, overcomes the limitations above mentioned @o make it possible to conduct large scale catalytic operations, above mentioned, in an eilicient and economic manner. In this invention a plurality ofA catalyst beds are employed connected for the series iiowof the reactants therethrough with provisions for heating or cooling the reactants as required (depending upon the endothermic or exothermic nature of the reaction) either as they pass from each catalyst bed to the next succeeding catalyst bed,-or and preferably as they pass from. one stage to the next succeeding stage. The design of the apparatus and conditions of operation are such that the temperature of the reactants does not rise or fall beyond allowable limits in passing through any stage of the series and such that the temperature of the reactantsis readjusted to the desired value as they pass from one stage to the other.

The improved method herein provided for conducting combinations Vof endother-mic reactions or exothermic reactions is not limited to any specic form or type of apparatus, but a great number of specific forms of apparatus may be devised to incorporate the ifeaturesoi! the invention. Neither is the invention limited to any speciflc combination of endothermic reactions 'or exothermic reactions of a catalytic type, since, as

evidenced by the examples 'above given, its advantageous features are applicable to a wide variety of specificloperations. However, to avoid confusion, the following description will be directed primarily to illustrating the features of the invention as applied to a combination involvasaaseo ing dehydrogenation and catalytic cracking ol.' hydrocarbon oils and further to periodic reactivation of the catalytic material employed.

In the accompanying drawings Figure l illustrates a simple form of apparatus embodying the broad features of the invention and in which the improved process provided by the invention may be conducted.

Figure 2 is essentially a flow diagram of a process for the treatment of hydrocarbons wherein said hydrocarbons are iirst subjected to dehydrogenation treatment followed by catalytic cracking treatment in a plurality of catalytic reaction zones connected in series, in each of which zones processing and reactivation of the catalytic material are' alternately accomplished with provision for controlling the temperature of the stream of reactants ilowing from each pair of catalyst zones to the next pair of catalyst zones of the series in which dehydrogenation is accomplished in the first zone followed by cracking in the second zone.

Figures 2A and 2B are enlarged sectional detail views of the four-way switching valves Vl' and V2' respectively, shown in Figures 2 and 3.

Figure 3 is a now diagram illustrating the modification of a portion of the ilow illustrated in Figure 2.

Referring to Figure l, reactor I is an elongated cylindrical column divided into a plurality of compartments 2 by means of solid partition plates l extending horizontally across the column. Each of the compartments 2 is provided with two perforated plates 4 and 5 which serve as supportingmembers for the beds of catalytic material 6 and 1, respectively, disposed in each of the compartments.l In the case here illustrated, bed

8 is composed of catalytic material capable of promoting the dehydrogenation reaction, while bed 1 is composed of catalytic material capable of promoting the cracking reaction.

A space is left on opposite sides of each of the partition plates 3, the upper space between perforated plate 5, 'and plate 3 4communicating through conduit 8 with an inlet of a suitable heater or heat exchanger 9 which discharges through line I0 into the space between plate I andthe next succeeding catalyst bed 6 which, in the case here illustrated, is composed of a dehydrogenating catalyst.

'I'he hydrocarbons to be treated enter the upper end of reactor I through line Il, preferably in essentially the vaporous state, and preheated -by well known means, not illustrated, toa temperature at which the desired reaction will occur upon contact with the catalytic material. These heated vapors pass downward through the ilrst or d ehydrogenation catalyst bed 6 in direct and intimate contact with the catalyst particles, and the dehydrogenation reaction accomplished in this bed reduces the temperature of the vapors undergoing treatment to some predetermined value. 'Ihe vapors leaving catalyst bed 6 at a Y lower temperature than the. entering vapors, the

asrdescribed above, are useful from the standpoint that dehydrogenation prepares an ideal charging stock for catalytic cracking, because from experiment it has beenv determined that oleilns may be 'cracked more readily than parmost suitable temperature conditions. `After Vleaving the bed of cracking catalysts,- the temstantially the same temperaturev as that prevailing vabove the first catalyst bed, Vbut preferably to `a higher temperature, since the reactants become more refractory as the reaction proceeds.

The reheated vapors are supplied to the second compartment 2 wherein they pass rst through a bed of dehydrogenation catalysts 8 and then to the next succeeding bed- `o f cracking catalysts 1. .Since .there isy a small temperature drop in each compartment, the. vapors leaving each com-- aillns. In addition, a sequence of reactions per- .mits each reaction to be carried out under the conversion zone (i. e., one dehydrogenation zone and one cracking zone), while the catalyst in the corresponding reactors of each group isf being reactivated bypassing therethrough a stream of hot relatively inert gases, (such as vcombustion gases, for example), containing controlled amounts of air or oxygen. Each pair of reactors in each group is alternately operated with respect to the service for which they are employed (processing and reactivation), byVv means of inlet switching valves VI and V2 and the outlet switching valves VI and V2'.

Any suitable valve arrangement capable of Y switching the direction of flow of the stream of reactants and the stream of reactivating gases may be employed withinthe scope of the inventiony and, for the sake of simplifying the description` and illustrating the process without unsucceeding beds, and the final conversion products are directed from the lower portion ofthe v reactor through" conduit I2 to suitable 'separating and recovery equipment, not illustrated.

It is, of course, within the scope of the invention to' employ any required ,number of beds of catalytic material through which the reactants are passed-in series, the size of each bed, and more specifically the beds in each compartment, being suillciently small in proportion to the volume of vapors passing `therethrough in 'a given time, that the temperature drop is not excessive.

The temperature of .the reactants is maintained withinthe range ofthat required for best results.

The various beds of catalytic material may be ed in series and provision being made for reheating the reactants-as they pass from each catalyst bed, but preferably from each group of catalyst beds to the next lsucceeding group.

Referring now vto Figure 2, previously'men- A .tioned, it is essentially a flow diagram of a process employing the features of the invention. In

the particular case here illustrated; two groups or. a total of eight catalytic reactors, there being four toeach group, are employed, the flrstpair in theflrst group beingdesignated as A -and A'.

the second pair in the rst group as B and B',

the first pair in the second group as C and C',

` and 'the second pair in the second group as D Y relation to the volume of vapors to be cracked f vin a given time that the drop in temperature sustained by the vapors in their passage through the bed is not excessive, (i. e., .the temperature range of the'vapors entering the bed yand leaving the bed is within thellmits of the temperature range at which active dehydrogenation or catalytic cracking of thejvapors will occur).

Two reactors of each group are employed as a necessary complications, each of the switching valves is here illustrated as a single four-way valve in which the position of the two passageways therethrough may be shifted as illustrated in Figures `2A and 2B. Assuming that inlet valves VI. and V2 are each adjusted to the position illustrated in Figure 2A, and outlet switching valves VI' and V2 are each adjusted to the position illustrated In Figure 2B,'the stream of hydrocarbon vapors heated'and vaporized in a suitable heating zone, not illustrated, and is suppliedto the system through line I3, flows through valve VI into line It andv thence to reactor A. After being subjected to contact with a dehydrogenat-ion catalyst in reactor- A, the vapors are directed through line I5 into reactor B and contacted therein 'with a cracking catalyst. The vapors leaving reactor B are directed through line I6 and valve VI wherethrough they pass to line Il 'and thence to heater HI', which may be any suitable form of heater or heat exchange device capable of reheating the vapors to substantially the sameor to a higher temperature than that prevailing in line I3. The reheated vapors are directed from heater HI through line 2| to valve V2 wherethrough they pass into line 22y and thence to reactor C. .After passing through the bed of catalytic materialjn reactor C, the partially cooled vaporsare directed through line '23 into reactor D and the -cooler vapors from reactor D vdirected through line 2 4 to` valve V2' wherethrough they pass into line 25 by' mea'ns of which they are conveyed' to suitable separating and 'fractionating equipment -or to any desired further treatment. Thus the l vapors to be converted, instead of passing through two relatively large catalyst beds in inthe absence of means, such as previously mentioned, for'preventing the same, they are passed in series through smaller catalyst beds wherein the temperatln'e drop 'is not excessive. vapors are reheatedlto the desired degree as they passfrom each group-of reactors to the next successive group, the. reaction temperature being therebymaintained within the optimum limits during the entire catalytic reaction.

Although I have illustrated a process employing only two groups of catalytic reactors, it is,

of course, within the scope of the invention to employ more than two groups in order to obtain the desired results.

With the flow of hydrocarbon vapors through reactors A, B,-C. and D, in the manner above d escribed, reactivating gases supplied to the system which the temperature drops would be excessive through branch lines i9 and 26 to the respective valves VI and V2 wherethrough they pass in to respective lines I4 and 22' and thence to the respective reactors A' and C wherein they contact the beds `of catalytic material disposedin these zones which have become fouled or partially spent by previous use. The deleterious deposits of carbonaceous material are thereby burned from the catalyst beds, the rate of burning being regulated by the oxygen content of the reactivating gases which is controlled to prevent thedevelopment of excessive temperature in the catalyst bed.

The reactivating gases from reactors A' and C' areV directed through the respective lines i5 and 23' to respective reactors B' and D' in order to remove by combustion the carbonaceous deposits on the catalyst of the latter two reactors. 'I'he resulting spent reactivating gases and combustion products are directed from the respective reactors B' and D through respective lines I6' and 24 to the respective outlet switching valvesl VI' and V2' wherethrough they pass to the respective lines and 21 into line 28.

'I'he temperature of these gases will be increased by the exothermic reaction (burning of the carbonaceous material) in the reactor, and preferably useful heat recovered therefrom 4for any required purpose and in any desired manner, not illustrated, following which the resulting cooled gases may be wasted or, when desired, they may be recirculated by means of a suitable pump or compressor, not shown, to line I8 and therein commingled with controlled amounts of air for supporting combustion, lthe latter being supplied v v in any desired manner. In this manner, the inert components of the reactivating gases may be continuously recycled through the system, but it is also within the scope of the invention, when desired, to continuously generate fresh combustion gases, for example, or steam for this purpose, by well known means not illustrated.

In the following operation, above described,- when the catalyst in reactors A, B, C, and D approaches the state of reduced activity, at which time it is advantageous to employ freshly regenerated catalyst for treatment of the vapors, the supply of air to the reactivating gas stream is momentarily discontinued so that thev reactors A', B', C', and D' are purged of oxygen-containing gases while the inlet and outlet switching valves remain in an unchanged position.- Immediately following this purge of reactors, A', B', C', and D', the position of the inlet switching valves VI and V2 is shifted to that indicated in Figure 2B, while the supply of air to line Il is still discontinued so that reactors A, B, C, and

D are purged of hydrocarbon vapors and the stream of vapors from line il is diverted to reactors A', B', C', and 'D'. After a time sumcient to allow purging of each of the reactors, the positions ofV outlet valves VI' and V2' are shifted to .that indicated in Figure 2A and air is again admitted to line Il whereupon the catalytic material in reactors A, B, C, and D is reactivated and the catalytic material in reactors A', B', C', and D' is utilized to promote conversion of 'the vapors supplied thereto.

Switching of the stream of hydrocarbon vapors and reactivating gases is periodically repeatediby reversing the position of .the switching valves so that the partially spent catalytic material in one pair 'of reactors of each group is continuously being reactivated and the stream of hydrocarbon vapors is continuously converted in the other pairs of reactors of each group. Preceding` the change of function in each pair of reactors, the reactors are purged with relatively inert gasesand, preferably, as indicated in the foregoing description, there is a sumcient delay between the switching of the inlet valves and the switching of the outlet valves to prevent the loss of valuable conversion products from the reactors being purged thereof and to prevent the commingling of inert gases from `the reactors which have been purged with the stream of conversion products. Also, the operation of the valves on the l.various pairs of reactors of each group are correlated to prevent the commingling of reactants or conversion products with reactivating or purging gases, (i. e., valves VI and V2 are first switched, and after a delay corresponding to the timeV required to purge reactors A, B, C, and D or reactors A', B', C', and D. valves VI' and V2 are simultaneously shifted).

When desired, instead of changing the function of each pair of reactors in the several stages simultaneously, a change of ,function may be effected only between the two .pairs of. reactors in each stage at any one switching operation, in which case the position of only two switching valves would be changed at each switching period; For example, when it isl desired to effect a change of function between reactors A and B and A' and B', valve Viis first switched, and after a delay correspondinglto the time required to purge reactors A, B, A', and B', the position of valve VI' is shifted, while valves V2 and V2' remain substantially-in the same position. Likewise, at the next switching period the positions of valves V2 and V2' would be shifted, while the positions of valves VI and VI' would Aremain unchanged.

The switching valves may be manually operated, but preferably to simplify operation of the process and to avoid mistakes in operation of the valves which might prove disastrous, both the inl is not a novel part of the present invention.` For the sakeof avoiding unnecessary complications,

automatic control means are not illustrated.

Several forms of time cycle controllers capable vof accomplishing the desired results are now in ngures 2 and als that in the latter the reactivating gases pass in series through the reactors in which the catalytic material is beingA reactivated, and provision is made for cooling. these gases as they pass from the mst pair of reactors wherein reactivation is taking place to the next succeeding pair of reactors.

In Flgure 3 the reactivating gases are supplied in the heated state through line Il to'valve Vl with the switching valves Vl and V2 in positions shown in Figure 2A and valves Vl and V2' in the positions shown in Figure 2B. The reactivating gases vpass through valve'vl -to line Il', thence through yreactors A' and B', and the resulting spent reactivating gases and combustion products from reactor B are directed through line I6' to valve VI wherethrough 'they pass to line 20 and thence to'cooler TI which may comprise anyv suitable type of heat transfer equipment capable of reducing the temperature of the gases to subn stantially the same as that to which they are supplied to reactor A.

Regulated quantities of vair are added to the stream of relatively inert gases passing through line 24' to valve V2 wherefroin they pass through line 21 to suitable lheat recovery equipment, not il1ustra'ted, or elsewhere as desired.

When the position of the switching valves is reversed so that valves VI and V2 are in the position illustrated in Figure.2B, valves VI and V2 are in the position illustrated in Figurev 2A, the oxygen-containing reactivating gases enter reactors A and C from the respective valves VI and V2 through the respective lines I4 and 22 and the spent reactivating gases and combustion A products pass from reactors B and D to the respective valves VI' and V2 to the respective lines I6 and 2l, the path of the flow of the gases being otherwise the'same as previously described.

A The foregoing description relates particularly to a process involving a combination of only two.

individual reactions 'and types of contact materials. It is to be understood that the invention may be employed in a system involving more than two reactions where each of the reactions are to some extent dependent'on the others. In

-all cases, the dependency of the individual re-v actions o each other-is used in determining the particular sequence which the reactions follow to accomplish the desired results. n

The invention when applied to a process involving dehydrogenation' and catalytic cracking save results as follows:

Combined feed consisting essentially of 60% of charging oil, a 36 A. P. '1. gravity Mid-Continent gas-oil, and 40% of recycle oil was heated to a temperature of 930 F. The resulting vapors were subjected to contact with an aluminachromia catalyst under substantially adiabatic conditions and as a result thereof the temperature was lowered to 890 F. The vapors at a temperature of 890 F. were subjected to contact with an alumina-chromia-zirconia cracking catalyst, likewise under adiabatic conditions, and as a result thereof the temperature was lowered to 880 F. The conversion products from the last mentioned cracking treatment were heated to 960 F. and the resulting vapors were subjected to the successive treatments of dehydrogenation and catalytic cracking. As a result thereof, the temperature was lowered to 910 F. .The conversion products from the second stage were reheated to 990 F. and the resulting vapors again subjected` to the successive treatments of dehydrogenation and catalytic cracking, whereupon the conversion products'were subjected to fractionation for the separation ofgasoline boiling range hydrocarbons from intermediate conversion products and residue, the latter recoveredand the intermediate conversion products subjected to further treatment. fIhe gasoline boiling range hydrocarbons, corresponding toA approximately conversion per pass and approximately 66.6% by'volume of the charging oil, were recovered as products of the process.

Iclaim as my invention: g l

l. A hydrocarbon oil conversion process which comprises passing the oil through a iirst converj sion sequence and therein subjecting the same to catalytic dehydrogenation'and then to catalyticl cracking, then heating the hydrocarbons to def hydrogenating temperature and introducing the same to a second conversion sequence, and sub'- jecting the hydrocarbons in the second sequence to catalytic dehydrogenation and to catalytic cracking in the orderinamed'. I

2. A catalytic conversion process which com- 4 prises passingf a stream of hydrocarbons through at least two like reaction sequences, each containing a plurality of vserially arranged catalyst bodies, in eachloi said sequences effecting catalytic dehydrogenation and. catalytic cracking in the order named in the presence of said catalyst y y b pdies, and, `as the hydrocarbon stream passes from one sequence to the next succeeding sequence,l readjusting its temperature to the hydrocarbon conversion temperature of saidsucceeding 1 Sequence' LOUISS.KASSEL. 

